Direct observation of the quantum tunneling of single hydrogen atoms with a scanning tunneling microscope

Single hydrogen atoms were imaged on the Cu(001) surface by scanning tunneling microscopy (STM). The vibrations of individual H and D atoms against the surface were excited and detected by inelastic electron tunneling spectroscopy (STM-IETS). Variable temperature measurements of H atom diffusion showed a transition from thermally activated diffusion to quantum tunneling at 60 K. Regimes of phonon-assisted and electron-limited quantum tunneling were observed. The thermal diffusion rate of D atoms varied over 7 orders of magnitude between 80 and 50 K with no transition to quantum tunneling down to a thermal hopping rate of 4x10(-7) s(-1).     

Control and characterization of a multistep unimolecular reaction

Electrons from a scanning tunneling microscope were used to break a C-H bond in a single acetylene (HCCH) molecule adsorbed on Cu(001) at 9 K. The product ethynyl (CCH) was characterized by imaging, inelastic electron tunneling spectroscopy, and variable temperature measurements of the rotation rate. Significant changes in the vibrational spectra and bonding geometry accompanied HCCH dissociation. The ethynyl was further dehydrogenated to form dicarbon (CC). Dissociation studies of the isotopes HCCD and DCCD permitted unambiguous identification of the reaction products.     

An Experimental Setup for Combined In-Vacuo Raman Spectroscopy and Cavity-Interferometry Measurements on TMDC Nano-resonators

Experimental Mechanics - Nanoelectromechanical (NEMS) systems fabricated using atomically thin materials have low mass and high stiffness and are thus ideal candidates for force and mass sensing...     

Symmetry selection rules for vibrationally inelastic tunneling

A combined experimental and theoretical study is presented for the C-D stretch mode excitation of acetylene isotopes, C2HD and C2D2, on Cu(100) via inelastic electron tunneling (IET) in a scanning tunneling microscope junction. The calculated IET images using density functional theory show that the measured signal from C2D2 derives from the antisymmetric stretch mode. Selection rules are derived and involve the constraint imposed by the IET image on the symmetry characters of the vibrational mode and the adsorbate-induced electron states at the Fermi level.     

Tomographic analysis of dilute impurities in semiconductor nanostructures

We describe the application of pulsed-laser atom probe (PLAP) tomography to the analysis of dopants and unintentional impurities in Si and Ge nanowires grown by the vapor–liquid–solid mechanism. PLAP tomography was used to determine the concentration of phosphorous in Ge nanowires and B in Si nanowires, enabling comparisons of the atomic concentrations of the reactants with those of the reaction products. Oxygen impurities were also detected, but the contribution from background gas adsorption was not ruled out. Gold catalyst impurities were not detected, and an upper bound of 5 ppm was established. Intrinsic and extrinsic origins of the detection limits of dopants and other impurities are described in detail. A tapered nanowire geometry was found to improve the mass resolution and signal-to-noise ratio by increasing the tip cooling rate. Simulations of nanowire cooling under laser pulsing were used to validate this improved approach to PLAP analysis of nanowires.     

Efficient preparation of 2,4-diaminopyrimidine nucleosides: total synthesis of lysidine and agmatidine

An efficient route for the synthesis of 2,4-diaminopyrimidine ribosides from cytidine is described consisting of six steps with overall yields >50% and only one chromatographic step. The key amine addition step utilizes LiCl and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) to ensure clean conversion to a single tautomeric product. This route has been used to prepare the modified tRNA nucleosides lysidine and agmatidine in quantities suitable for structural characterization.     

Vibrationally mediated negative differential resistance in a single molecule

Negative ion density fronts have been shown to occur in electronegative steady-state plasmas with hot electrons. In this Letter, we report theoretical and numerical results on the spatiotemporal evolution of negative ion density fronts during plasma ignition and extinction (afterglow). During plasma ignition, the negative ion fronts are analogous to hydrodynamic shocks. This is not the case during plasma extinction where, although negative ions diffuse freely in the plasma core, the negative ion front propagates towards the chamber walls with a nearly constant velocity.     

RNA aptamers that bind flavin and nicotinamide redox cofactors

RNA molecules that specifically bind riboflavin (Rb) and beta-nicotinamide mononucleotide (NMN) have been isolated by in vitro selection. A simple structural motif containing intramolecular G-quartets was found to bind tightly to oxidized riboflavin (Kd = 1-5 micromolar). DNA versions of the consensus sequence also bind, but with weaker affinity. DMS protection experiments show that the quartet structure of these aptamers is stabilized by interaction with the flavin. As a measure of their redox specificity, the aptamers do not show significant differential binding between oxidized and reduced forms of a 5-deazariboflavin derivative that is a close structural analog of riboflavin. In contrast to the lack of redox specificity of the riboflavin aptamers, RNAs selected for binding to the nicotinamide portion of NAD discriminate between NAD and NADH in solution by over an order of magnitude. A mutagenized pool based on one of the NMN aptamer sequences was used to reselect for NMN binding. Comparison of the reselected sequences led to the identification of the binding region of the aptamer. A complex secondary structure containing two interacting stem-loops is proposed for the minimal NMN-binding RNA. The same mutagenized pool was used to select for increased discrimination between NMN and NMNH. From these reselected sequences, a mutation within the binding region was identified that increases specificity for NMN. These experiments show that RNA can bind these cofactors with low micromolar affinity and, in the case of nicotinamide cofactors, can discriminate between the two redox states. These cofactor binding motifs may provide a framework for generating new ribozymes that catalyze redox reactions similar to those found in basic metabolic pathways.     

Composition analysis of single semiconductor nanowires using pulsed-laser atom probe tomography

We report the composition analysis of single InAs and Si semiconductor nanowires using pulsed-laser atom probe tomography. The experimental conditions and sample geometries needed to realize 3-D composition mapping are described in detail. InAs mass spectra obtained using voltage pulses and laser pulses are compared, and are found to be superior for pulsed-laser evaporation. The ability to analyze intrinsic Si nanowires using pulsed laser evaporation is demonstrated. No peaks associated with the gold catalyst used were found in the InAs or the Si nanowire mass spectra. PACS 68.70.+w; 61.82.Fk; 61.72.Ss